D. Gerrard Marangoni

2 Surfactants and their applications

Surfactants form a unique class of chemical compounds. This review provides an introduction to the nature and physical properties of surfactants, emphasizing their ability to radically alter surface and interfacial properties and to self-associate and solubilize themselves in micelles. These properties provide the means to apply surfactants in wettability modification, detergency, and the displacement of liquid phases through porous media on one hand, and to stabilize dispersions (including foams, froths and emulsions), or to destabilize dispersions (again including foams and emulsions) on the other hand. These in turn lead to a vast array of practical application areas which are illustrated in terms of mineral and petroleum processing, biological systems, health and personal care products, foods, and crop protection.

Spontaneous vesicle formation with an ionic liquid amphiphile

A simple and effective method for the formation of stable multilamellar vesicles is reported as a potential application of ionic liquid materials (ILs) and as replacements for conventional surfactants used in such applications. The methodology is based on the various approaches for the formation of vesicles from oppositely charged surfactants. Photon correlation spectroscopy (PCS) and transmission electron microscopy (TEM) have been used to estimate the size of the aggregates; the TEM studies have also revealed morphological differences in the self-assembled systems with changing ionic liquid material. Size measurements from PCS indicate consistent growth of the ionic-liquid containing vesicles with increasing concentration of added anionic surfactant. 2D NOESY NMR spectroscopy have been used to examine the manner in which IL amphiphile self-assembles with the second surfactant in solution. A comparison has been made between the aggregates formed from hexylpyridinium tetrafluoroborate ([HexPy][BF4-])/sodium dodecylsulfate (SDS) and hexylpyridinium bromide ([HexPy][Br])/sodium dodecylsulfate (SDS).

MICELLE FORMATION, RELAXATION TIME, AND THREE-PHASE COEXISTENCE IN A MICROEMULSION MODEL

Our Larson‐type microemulsion model for surfactant chains in oil–water solvents leads to long relaxation times as well as, for essential modifications, to a stable peak in the chain‐cluster size distribution. Transfer energies for surfactant chains moving to the oil–water interface, and characteristic micelle concentrations (CMC) as a function of chain length are compared with experiment.

Synthesis of surfactants based on pentaerythritol. I. Cationic and zwitterionic gemini surfactants.

Simple strategies for the synthesis of five series of cationic gemini surfactants and one series of zwitterionic gemini surfactants from pentaerythritol have been developed. Two lipophilic groups were introduced onto pentaerythritol by alkylation of the known compound, O-benzylidenepentaerythritol, with 1-bromooctane, 1-bromodecane, 1-bromododecane, and 1-bromotetradecane. Hydrogenolysis of the benzylidene acetals gave diols which were converted into three different series of trimethylammonium derivatives. The diiodides derived from the diols could be displaced by dimethylamine, even though they are adjacent to a quaternary carbon atom. Alkylation with methyl iodide gave the first series. The iodides were easily displaced by cyanide ion and the resulting dinitriles were hydrolyzed, converted to N,N-dimethylamides, and reduced to give a second series. Oxidation of the diols to dialdehydes under Swern conditions followed by Horner-Wadsworth-Emmons reactions with diethyl N,N-dimethylcarbamoylmethylphosphonate followed by two-stage reduction gave a third series. The dialkoxides derived from the four di-O-alkylpentaerthritol diols were reacted with 2-dimethylaminoethyl chloride and 3-dimethylaminopropyl chloride in neighboring-group assisted double Williamson ether syntheses to give precursors to two more series. As expected because the neighboring group participation occurs through a four-membered-ring intermediate, considerably more vigorous conditions were required for the reactions with 3-dimethylaminopropyl chloride. 2-Diethylaminoethyl bromide was found to be less reactive than 2-dimethylaminoethyl chloride. The products were alkylated with methyl iodide and, in some cases, other alkyl halides to give cationic gemini surfactants. Alkylation of one series with ethyl bromoacetate followed by anion exchange resin catalyzed ester hydrolysis gave zwitterionic gemini surfactants. The members of all series have superior surfactant properties.

Mixed aggregate formation in gemini surfactant/1,2-dialkyl-sn-glycero-3-phosphoethanolamine systems.

An evaluation of the physical interactions between gemini surfactants, DNA, and 1,2-dialkyl-sn-glycero-3-phosphoethanolamine helper lipid is presented in this work. Complexation between gemini surfactants and DNA was first investigated using surface tensiometry where the surface tension profiles obtained were found to be consistent with those typically observed for mixed surfactant-polymer systems; that is, there is a synergistic lowering of the surface tension, followed by a first (CAC) and second (CMC) break point in the plot. The surfactant alkyl tail length was observed to exhibit a significant effect on the CAC, thus demonstrating the importance of hydrophobic interactions during complexation between gemini surfactants and DNA. The second study presented is an investigation of the mixing interactions between gemini surfactants and DOPE using Clints, Rubinghs, and Motomuras theories for mixed micellar formation. The mixing interactions between the 16-3-16/16-7-16/16-12-16/16-7NH-16 gemini surfactants and DOPE were observed to be antagonistic, where the strength of antagonism was found to be dependent upon the gemini surfactant spacer group and the solution composition.

Solubilization equilibria of alcohols and polymers in micellar solutions: NMR paramagnetic relaxation studies

Abstract The solubilization equilibria of some typical alcohols in cationic, anionic, and nonionic surfactant micellar solutions were investigated using the NMR paramagnetic relaxation method [J. Phys. Chem., 93 (1989) 2190]. The degree of solubilization of solubilizate in the micellar phase, p , was determined by monitoring the change in the 1 H spin-lattice relaxation rate of the solubilizate upon the addition of paramagnetic ions to the aqueous phase. Hydrophilic paramagnetic ions, which should have the same sign of charge as the micellar surface for the case of ionic surfactant systems, were used to enhance the spin-lattice relaxation rate of solubulizate in the aqueous phase. The degree of solubilization obtained is, within experimental error, independent of the concentration of the paramagnetic ions. The error in the degree of solubilization, p , decreases with increasing paramagnetic ion concentration. The results obtained using different paramagnetic ions (i.e., 3-carboxylate-PROXYL (charge: − 1) and Mn (EDTA) 2− in anionic micellar systems, and Mn (D 2 O) 2+ 6 and Mn (EDTA) 2− in nonionic micellar systems) are in good agreement. The paramagnetic relaxation method was also used to determine the degree of solubilization of poly (ethylene oxide) in two surfactant solutions, sodium ω-phenyldecanoate and sodium dodecyl sulfate.

Surfactants: Surfactants and Their Solutions: Basic Principles

This chapter provides an introduction to the occurrence, properties and importance of surfactants as they relate to the petroleum industry. With an emphasis on the definition of important terms, the importance of surfactants, their micellization and adsorption behaviours, and their interfacial properties are demonstrated. It is shown how surfactants may be applied to alter interfacial properties, promote oil displacement, and stabilize or destabilize dispersions such as foams, emulsions, and suspensions. Understanding and controlling the properties of surfactant-containing solutions and dispersions has considerable practical importance since fluids that must be made to behave in a certain fashion to assist one stage of an oil production process, may require considerable modification in order to assist in another stage. Introduction Surfactants are widely used and find a very large number of applications because of their remarkable ability to influence the properties of surfaces and interfaces, as will be discussed below. Some important applications of surfactants in the petroleum industry are shown in Table 1. Surfactants may be applied or encountered at all stages in the petroleum recovery and processing industry, from oilwell drilling, reservoir injection, oilwell production, and surface plant processes, to pipeline and seagoing transportation of petroleum emulsions. This chapter is intended to provide an introduction to the basic principles involved in the occurrence and uses of surfactants in the petroleum industry.

Nonaromatic Hydrotropic Cationic Ammonium Salts as a Rheology Modifier for an Anionic/Zwitterionic Surfactant Mixture

In this article, we report additive-induced micellar growth and rheology modification for mixtures of anionic (sodium dodecyl sulfate, SDS) and zwitterionic (N-alkylated glycine derivative, Empigen BB or EBB) surfactants. Two nonaromatic hydrotropic salts (hexyltrimethylammonium bromide, C6TAB, and/or dibutylenebis(dimethylbutylammonium bromide), 4-4-4) are used as novel additives to induce micellar growth in these systems. Nuclear magnetic resonance (NMR), photon correlation spectroscopy (PCS), transmission electron microscopy (TEM), the Weissenberg effect, and rheology measurements were employed to assess mixed micelle formation, micellar growth, and rheology modifications. Finally, the manner in which the surfactants and hydrotropes self-assemble into aggregates has also been deduced from 2D NMR NOESY measurements. In this study, both hydrotropic ions have been found to contribute to similar structural modifications in the mixed micelles of the anionic and zwitterionic surfactants. However, the extent of the rheology modification in solution is found to be quite different when the gemini hydrotrope (4-4-4) versus the monomeric hydrotrope (C6TAB) is employed.

Interactions between gemini and nonionic pharmaceutical surfactants

The nature and strength of the interactions between the 1,3-bis(dimethylhexadecyl)propanediammonium dibromide (16-3-16) gemini surfactant and a homologous series of nonionic polyoxyethylene (20) so...

1D and 2D NMR investigations of the interaction between oppositely charged polymers and surfactants

Proton chemical shifts and two-dimensional COSY and NOE spectroscopy (NOESY) experiments have been used to examine the interaction of various oppositely charged surfactant and polyelectrolyte systems, namely, the cationic surfactant dodecyltrimethyammonium bromide (DTAB) and a series of alkanediyl-α,ω-bis(alkyldimethylammonium bromide) surfactants (Gem 12-s-12, where s is the length of the methylene spacer group) with the anionic polyelectrolyte poly(styrene sulfonate) or PSS. In all cases, we observe substantial aromatic-solute-induced chemical shifts (ASIS) in the surfactant peaks of the polymer/surfactant complexes versus that of the pure surfactant spectra. In the case of the DTAB/PSS system, the chemical-shift changes as a function of changing ratio of surfactant to polymer are interpreted in terms of structural changes that occur in the complex with increasing polymer concentration. For the Gem 12-s-12/PSS systems, the interaction of these gemini surfactants with the anionic polyelectrolyte, as dedu...